Mn─O Covalency as a Lever for Na⁺ Intercalation Kinetics: The Role of Oxygen Edge‐Sharing Co Octahedral Sites in MnO₂

Abstract The strategic enhancement of manganese–oxygen (Mn─O) covalency is a promising approach to improve the intercalation kinetics of sodium ions (Na⁺) in manganese dioxide (MnO 2 ). In this study, an augmenting Mn─O covalency in MnO 2 by strategically incorporating cobalt at oxygen edge‐sharing Co octahedral sites is focused on. Both experimental results and density functional theory (DFT) calculations reveal an increased electron polarization from oxygen to manganese, surpassing that directed toward cobalt, thereby facilitating enhanced electron transfer and strengthening covalency. The synthesized Co–MnO 2 material exhibits outstanding electrochemical performance, demonstrating a superior specific capacitance of 388 F g −1 at 1 A g −1 and maintaining 97.21% capacity retention after 12000 cycles. Additionally, an asymmetric supercapacitor constructed using Co–MnO 2 achieved a high energy density of 35 Wh kg −1 at a power density of 1000 W kg −1 , underscoring the efficacy of this material in practical applications. This work highlights the critical role of transition metal–oxygen interactions in optimizing electrode materials and introduces a robust approach to enhance the functional properties of manganese oxides, thereby advancing high‐performance energy storage technologies.